N-(decachloro-3-hydroxypentacyclo(5.3.0.02, 6.05, 9)decyl-3) ureas



United States Patent Ofiice 3,314,991 Patented Apr. 18, 1967 3,314,991 N-(DECACHLORO-3-HYDROXYPENTACYCLO (5.3.0.0 10 .0 )DECYL-3) UREAS Edward D. Weil, Lewiston, and Keith J. Smith, Lockport,

N.Y., assignors to Hooker Chemical Corporation, Ni-

agara Fails, N.Y., a corporation of New York No Drawing. Filed Nov. 30, 1965, Ser. No. 510,659 6 Claims. (Cl. 260-553) ('31 (Ill (10 e u 4 Cl Cl R r i ii Cl OH X where R is a member selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, R is a member selected from the group consisting of hydrogen, allcyl, substituted alkyl, aryl, substituted aryl, amino, substituted amino, alkoxy, and aryloxy, X is an element selected from the group consisting of sulfur and oxygen, oxygen being preferred for reasons of cost and, generally, stability.

The group R or R may be of high molecular weight and either or both may in fact represent macromolecular chains; and the compositions of the invention may, therefore, be macromolecular (polymeric) substances as Well as lower molecular weight substances.

For the sake of simplicity the below portion of the generic formula given previously will be referred to as 1o 1o( Among the many compounds intended to be included within the scope of this invention are the following compounds. Because of the unsettled and difficult nomenclature, the compounds are represented structurally rather than by names.

C O OHzCHi CHz- X 1d related structures.

In the latter five structures as represents the degree of Jlymeriza-tion, greater than one and with no upper limit. hese macromolecular products of the invention may be tade by the same general process as the lower molecular eight products, and are characterized by the same type 5 anti-fouling activity, while at the same time retaining :rtain of the desirable physical properties of the parent .acromolecular compound, such as the ability to form lms. Being resins, these products may serve not only anti-fouling components of marine paints but also as lm-forming or film-reinforcing ingredients.

The foregoing list of compounds is merely intended to illustrative of the scope of this invention and is not in 1y sense intended to limit or define the invention.

While the causes of marine fouling are presently bscure, its effect on economic and military affairs is :adily apparent. It is estimated that the cost of preventig, slowing down and treating marine fouling runs into lllilOl'lS of dollars annually, and no satisfactory solution in sight. For example, the efliciency and the period t use of a pier, ship, boat, buoy or marine structure is reatly reduced unless some prophylactic treatment is allowed. Ships which have become encrusted with iarine organisms lose a substantial part of their normal peed and mechanical efficiency. Furthermore, many lips and marine structures such as bulkheads, buoys, offrore radar towers and oil drilling rigs and platforms nce foulded are much more prone to become corroded r rotted. For this reason, an extensive and costly proram of prophylaxis and maintenance is followed in an effort to cut down the even more expensive deleterious effects of the marine fouling.

The most common method of reducing the amount of the shell-like encrustation built up by the lower forms of marine life such as barnacles or other lower marine creatures is to paint the material to be protected with a special copper oxide based paint. However, the amount of copper oxide required adversely effects the physical characteristics of the paint and its normal life is reduced. In addition, the presence of a large quantity of copper oxide on a metal boat or ship will eventually create an electrolytic cell which greatly accelerates the tendency toward corrosion. To prevent this electrolytic corrosion the surface must first be covered by an additional and expensive coat of paint to insulate the copper oxide from the hull. But even when so protected, the hull of any ship or boat must be routinely scraped to remove the fouled surface which forms though albeit more slowly. Obviously too, this is expensive, since in addition to requiring costly and time-consuming dry-docking, scraping and repainting, the ship is removed from profitable use. For the above reasons, it can readily be seen that the discovery of compounds possessing anti-marine fouling properties at low concentrations is of extreme commercial and naval importance. While the mechanism by which the compounds of this invention retard marine fouling is not understood, it has been found that these compounds function well at economically feasible concentrations, are non-corrosive in themselves and being readily compatible with the oils, bases and adjuvant s commonly used in paints can readily be formulated in marine paints and coatings in general.

While the compounds of this invention are advantageous as anti-marine fouling agents, they posses in addition other important advantages. For example, the novel compositions of this invention are useful as fire retardants and mildew retardants when formulated in organic coatings.

In addition, these compostions may be used as intermediates in the preparation of other anti-fouling compositions. Thus, when CwC nK D- is heated with an excess of phthalimide, the product,

00 l CwCho N is produced. This compound also has activity as a marine anti-fouling substance.

A related but ancillary advantage that the compounds of this invention possess generally is that they are valuable intermediates for organic synthesis, in that the reactive and free OH group may be further replaced by -NRC(=X)R', where R, R and X have the same meaning as previously defined.

A further attribute that these compounds possess as synthetic intermediates is that in many instances they form complex addition compounds with water, amines, and even with additional moles of amide beyond the stiochiometrically combined amount. This characteristic is believed to be due to the ability of the -OH group to form a hydrogen bond with an electron-rich atom, particularly with a divalent oxygen atom or a trivalent nitrogen atom. For example, the product hydrated solid complex approximating to C Cl (OH)NHCHO-NH CHO-H O A further characteristic of the new compounds of the invention is that they have weak acidic properties, perhaps due to the --OH group but also in some cases perhaps due to the -NH-CO group. Regardless of the theoretical reasons, it has empirically been found that strong bases such as sodium methoxide, hydroxide, and the like can form salts with the compounds of the invention. Since the above mentioned salts and complexes can revert to the parent compounds of the invention, they constitute usable formulations for the purposes of anti-fouling coatings, a fact which we have empirically confirmed.

The novel compounds of this invention may be prepared by reacting hexachlorocycl-opentadiene with chlorosulfonic acid, then heating the intermediate that forms in an appropriate solvent with at least one molar equivalent of an amide or thioamide of the structure NHRC(=X)R'. The amide NHR(C=X)R may be added at the beginning of the heating, gradually during the heating, or after the heating has commenced for several hours. The rate and order of addition has not been found to be a critical feature of our process. It has also been found possible to employ polymeric compounds having a free and reactive structure NHRC(=X)R' as reactants, for example, proteins, nylon, partially or fully hydrolyzed acrylonitrile polymers or copolymers and the polyurethanes. Starting with macromolecular amides, macromolecular products are obtained. It is not necessary to use a solvent for the reaction when the amide NHRC(=X)R is a liquid or low melting solid, but where the amide is not easily fused, a solvent is convenient. Appropriate solvents include but are not limited to chlorinated hydrocarbons, such as chlorobenzene or acetylene tetrachloride, aliphatic and aromatic compounds such as cyclohexane, xylene or toluene; ketones such as methyl ethyl and methyl propyl ketone, ethers such as diethyl, dipropyl, isobutyl, nitrohydrocarbons such as the nitrobenzenes, esters such as the lower alkyl acetates, N,N-dialkylamides such as dimethylformamide and acids such as formic acid. Where the NHRC(=X)R is a liquid the solvent may be dispensed with using an excess of the amide or thioamide instead. The temperatures needed to initiate and continue this reaction are not critical and vary considerably according to the reactants used. However, the extremes have been found to be from about zero degrees centigrade to two hundred degrees centigrade with a satisfactory range generally being between twenty degrees and one hundred and seventy-five degrees centigrade. Similarly, the time for the reaction to become complete, as measured by infra-red analysis, varies according to several factors such as temperature and reactants. Many reactions are completed in less than an hour, but others occasionally take as long as a day. The reaction may also be followed by checking the rate of S whihc is evolved, the reaction being halted when the flow of S0 has substantially ceased. A variation of the above process is to use a nitrile or imide capable of being hydrolyzed to the desired amide NHR(C=X)R plus at least the stoichiometric quantity of water required for said hydrolysis, the hydrolysis being run concurrently with the reaction of the invention. The structures of the products are proved by elemental analysis by infra-red spectra which shows the OH group absorption and the characteristic amide C=O or thioamide C:S bands. The presence of the pentacyclo decane skeleton is proved by fusion with several parts by weight of PCl in a sealed tube at elevated temperatures, which yields the known dodecachloropentacyclo-(5.3.0.0 .0 .0

6 decane, melting point four hundred and eighty-five degrees. A more detailed discussion of the process and compositions produced is presented in the examples which follow.

Example 1.-Preparati0n 0f (C Cl (OH) (NHCOCH Hexachlorocyclopentadiene is reacted with chlorosulfonic acid as disclosed in US. Patent 2,516,404, an intermediate (described in said patent as C H O SCl is formed which has a melting point of one hundred and forty-six to one hundred and forty-eight degrees centigrade. This intermediate is a definite chemical entity of melting point one hundred and forty-six to one hundred and forty-seven degrees and having a chlorine content of 67.8 percent and sulfur content of 5.09 percent. Because of its high molecular weight (six hundred and eleven to six hundred and thirty-nine) and difficult combustibility, the number of hydrogen atoms in the molecule is in doubt, and consequently its exact structure is uncertain. A solution of 62.8 parts by weight of this compound and 5.9 parts by weight of acetamide in one hundred and seventysix parts by weight of xylene is refluxed for six hours until evolution of S0 had substantially dwindled. The solution is concentrated and the resultant crystalline product removed by filtration and dried in air. An infrared spectrum showed the compound to have an -OH group, an -NH group, an amide C=O group, and a methyl group.

Analysis.-Calcd. for C Cl (OH) (NI-ICOCH Cl, 64.5; N, 2.5., Found: Cl, 63.5; N, 25.

Upon heating the product for twenty-four hours at three hundred degrees centrigrade with an excess of phosphorus pentachloride in a sealed tube, and evaporating the reaction mixture under vacuum at one hundred degrees centigrade, the volatile substances are removed leaving a crystalline substance which upon recrystallization, melts at four hundred and eighty-five degrees centigrade, which is the melting point of the expected and known derivative dodecachloropentacyclo-(5.3.0.O .O .0 decane, and has the correct percentage of chlorine for C Cl Example 2.Preparati0n of C Cl .(OH) (NHCHO) NC HO hydrate One part by weight of the intermediate chlorosulfonation product of Example 1 melting at one hundred and forty-six to one hundred and forty-eight degrees centigrade is dissolved in ten parts by weight of forma-rnide at one hundred degrees centigrade. After twenty-four hours at this temperature, the reaction mixture is cooled and poured into distilled water. The colorless crystalline product which precipitates out, is filtered otf and air dried. Infra-red analysis shows the presence of the desired -OH, -NH and amide C=O groups, as Well as an additional shoulder in the carbonyl region Analysis. Calcd. for C Cl (OH) (NHCHO) NHCgIO) -H O: Cl, 59.7; N, 4.7. Found: Cl, 60.7; N, 4.

ONOIMOH) (ITIOOCHzCHzCHzCHzCILCHs) 62.8 parts by weight of the product of hexachlorocyclopentadiene and ClSO H, melting at one hundred and forty-six to one hundred and forty-eight degrees centigrade, of Example 1, is refluxed one day with 11.3 parts by weight of 2-oxohexamethyleneimine(caprolactam) in one hundred and seventy-six parts of xylene. On cooling to room temperature, there precipitates a colorless crystalline material, the infrared spectrum of which shows -OH, lactam C=O, but no -NH, which is the spectrum one would expect for the desired product.

Analysis.Calcd. for

In two hundred and sixty-four parts of xylene, 12.1 parts by weight of benzamide is reacted with 62.8 parts v weight of the crystalline C Cl /ClSO H product, melt- .g at one hundred and forty-six to one hundred and fortyght degrees. After four hours, the S evolution windles. On partial evaporation of the xylene and coolig, a colorless crystalline product is obtained whose tfra-red spectrum showed -OH, -NH and amide @O :oups as well as C=C double bond vibrations charactertic of an aromatic ring.

Analysis.-Calcd. for C Cl (OH)(NHCOC H Cl, 8.0; N, 2.3. Found: Cl, 57.9; N, 2.3.

It is found possible to titrate the product in acetone )lution using tetrabutylammonium hydroxide (0.1N) s the base. The end point occurs at the point where one iolar equivalent of the base is added, showing that the f Cl (O'H)NHCOC H is a monobasic acid.

Example 5 .--Preparati0n of C C1 (OH)NHCOC H A mixture of 62.2 parts of octadecylamide (ten perent molar excess), one hundred and twenty-five parts of 1e crystalline product of hexachlorocyclopentadiene and hlorosulfonic acid, and two hundred and twenty parts of ry xylene are heated at reflux for one day, until S0 volution dwindled. The xylene is evaporated under rater-aspirator vacuum and the waxy residue recrysallized from heptane and a white waxy solid is obtained, ielting point seventy to seventy-five degrees.

Analysis.-Calcd. for C H O NC1 N, 1.8. Found: I, 1.9.

Example 6.Preparatio n of C10Cl10(OH)NHCO(cH2)1CH CH(CH2)7CH3 As above, using 61.8 parts of oleamide (ten percent iolar excess). The residue on evaporation of the xylene a liquid and cannot be induced to crystallize.

The infra-red spectrum confirmed that the product has he tructure.

Example 7.-Preparati0n of C Cl (OH)N(COCH )C H A mixture of 62.8 parts of the crystalline reaction product of C Cl and ClSO H is heated with 13.5 parts If acetanilide in one hundred and eighty parts of xylene tt reflux for six hours, until S0 evolution dwindles. Dooling to room temperature gives a crystalline precipiate, 30.5 parts by weight. Its infra-red spectrum shows he characteristic amide carbonyl band at six microns.

Analysis.Calcd. for C Cl (OI-I)N(COCH )C H 31, 56.7. Found: Cl, 57.9.

Example 8.Preparati0n 0f C Cl (OI-I)NHCHO A mixture of 31.3 parts of the crystalline reaction )roduct of C Cl and ClSO H in one hundred and seventy- :ix parts of xylene, mother liquor from a previous preparaion of C Cl (OI-I)NHCHO, is refluxed for several 10111'S, then while maintaining reflux, 9.0 parts of formimide is added and reflux continued for thirty hours.

8 The mixture is then cooled to twenty to thirty degrees, and the resulting crystalline precipitate filtered off. The mother liquor is employed for a repeat run. The crystalline precipitate melts at three hundred and thirty-six degrees. Analysis.Calcd. for C Cl (OH)N-HCHO: N, 2.6. Found: N, 2.6.

A mixture of 62.8 parts of the crystalline product of C Cl and ClSO H and 26.8 parts of furarnide in one hundred and seventy-six parts of xylene are refluxed for one day at the end of which time S0 evolution is negligible. On cooling, a dark amorphous precipitate is formed which is filtered and dried. The infra-red spectrum supports the structure, although some complexed or entrained furamide appeared to be present. The product is used in the crude form.

Analysis.Calcd. for

C chuwH)oOo=oH-cH=CH9 N, 3.7. Found: N, 4.2.

Example 10.-Preparati0n of C Cl (OH)NHCOCH C H A mixture of 62.8 parts of the crystalline product of C Cl and ClSO H in one hundred and seventy-six parts of xylene is refluxed for one day with 13.5 parts of aphenylacetamide. On cooling, a precipitate is obtained which, by infra-red, is established -to have the desired C Cl (OI-I)NHCOCH C H structure.

Analysis.Calcd. for C Cl (OH)NHCOCH C H N, 2.2. Found: N, 2.25.

Example 11.Preparation of C Cl (OH)- substituted polyam ide Example 12.Preparati0n of other representative compounds of this invention The chlorosulfonic acid intermediate of hexachlorocyclopentadiene melting at one hundred and forty-six to one hundred and forty-eight degrees centigrade is reacted with the appropriate amide as disclosed in the preceding examples. The following compounds are prepared (left hand column), in crude form. The right hand Column gives the amides used.

Compound Derived Fr0m Salicylamide.

Example 13.--Formulation of marine paint having antifouling properties The following ingredients are blended and ground toether in a ball mill.

ngredient: Pounds per 100 gallons Gurn rosin, grade WW 277 Blown fish oil 118 Zinc stearate 18 Versamide polyalmide adduct of Example Zinc oxide 161 Magnesium silicate 56 Solvent naphtha (approx) 1 241 Lampblack 1 1 Volume adjusted to 100 gal. by addition of naphtha.

Example 14.Frmalati0n of marine paint having antifoaling properties The following ingredients are blended and ground together in a ball mill.

ingredient: Pounds per 100 gallons Rosin 3 11 Hydrogenated methyl abietate 115.5 Coal tar naphtha 92.4

Mineral spirits (paint thinner) (approx) 1 103.7

Diatomaceous silica 103 .7 C Cl -(OH)NHCOC H 311 Lampblack 1.0

1.2 Example 17.-An0ther formulation of marine paint having antifoaling properties The following ingredients are blended together in the denoted proportions, in a roller mill.

Ingredient: Percent by weight Chlorinated rubber (Parlon 8-125) 2.5 Rosin 20.00 Dibutyl phthalate 0.30 Titanium dioxide pigment 21.65 Zinc oxide 8.55 Cobalt naphthenate 0.05 Lead naphthenate 0.19 Phenoxypropylene oxide 0.13 C Cl (OH)NCOC -;H from Example 5 5.00 Xylene Remainder Example 18.Testing of paint formulations of the preceding examples for an tifouling properties The formulations disclosed in the preceding examples are painted on steel test panels, allowed to dry and immersed in sea water at a sub-tropical location. At the same time other identical panels are painted with control test formulations identical with these paint preparations except that the N-decachlorohydr-oxypentacyclodecylamide derivatives are omitted from the formulation. These test panels are immersed in the same sub-tropical sea water. After one month both the control test panels and the panels containing the active component are examined and compared. It is found that the control panels are heavily crusted with a mixed population of barnacles and other marine organisms, while the panels containing the active anti-marine fouling component were not adversely affected.

Example 19.Testing of anti-marine fouling properties of difierent products of this invention To eliminate variables due to the other ingredients in the paint formulations a simplified comparison test is carried out by treating porous test panels with a number of the products of this invention applied as a three percent Ingredient: Pounds per 100 gallons solution of methyl isobutyl ketone. The panels are al- Rosin 265 lowed to dry and are then immersed in sea water at a Coal tar -a 80 sub-tropical location where untreated test panels became Talc heavily fouled during the test interval. After a one month Pine oil 42 period the degree of fouling control was observed ac- C CI (OH) (NHCOCH from Example 1 200 cording to the amounts of fouling organisms found on the High flash naphtha 135 treated panel surface compared to identical untreated Mineral spirits Make up to volume 50 panels. The results are recorded on Table I below,

TABLE I.PERCENT CONTROL OF FOULING BY INDICATED ORGANISMS Compound Algae Amphipods Annelida Barnacles Bryozoa Hydroids Mollusks Tunicates Microfouling C1 O1w(OI-I)(NHCHO) 100 100 100 100 100 100 100 10 CwClw(0H)(NHCOGH3) 100 100 100 95 100 100 100 108 OwC1|u(OH)(NIlCOCul-l5) 100 100 100 100 100 100 100 100 100 CWOIMOH)(NHCOCHZCBHS) 50 100 100 100 100 100 100 100 C10C110(O:H)(NHCONI'I2) O 0 2O 0 0 50 100 50 0 CioCliu(OH)N OmC1m(OH)NI-IC 0l 100 100 50 0 0 70 100 0 70 What is claimed is: sisting of amino and lower alkyl-subsztituted amino and X 1. is selected from the group consisting of oxygen and sulfur. C1 C1 2. A compound according to claim 1 wherein X is oxygen.

3. A compound according to claim 1 wherein R is amino. 4. A compound according to claim 3 wherein R is C1 I lk hydrogen and R is NH 5. A compound according to claim 2 wherein R is amino. 01 c1 /01 1O 6. A compound according to claim 5 wherein R is C hydrogen.

1 No references cited.

where R is selected from the group consisting of hydrogen '15 ALEX MAZEL Primary Exammer' and lower alkyl, and R is selected from the group con- H. R. JILES, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,314,991 April 18, 1967 Edward D. Weil et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, lines 34 to 37, the formula should appear as shown below instead of as in the patent:

3 (1 C1 (0H) N\C O(CH CH column 4, line 34, for "posses" read possess line 39, for "compostions" read compositions column 5, line 4, after the formula insert a period; line 59, for "whihc" read which column 6, line 30, for "centrigrade" read centigrade line 41, for "NC HO" read NH CHO line 56,

for

"c cl wm( COCH CH CH CH CH JH read Example 3.-

Preparation of C Cl [OH)(IPJCOCH CH CH CH CHIH column 8,

line 18, the formula should appear as shown below instead of as in the patent:

(1 C1 (OH) NHCOC=CH-CH=CHO same column 8, line 36, for "2.25" read 2.5 4 columns 9 and 10, in the table, first column, the sixth compound thereof should appear as shown below instead of as in the patent:

(3 C1 (OH)-N Signed and sealed this 3rd day of December 1968.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

